Natural Gas Conversion VIII (eBook)

Cover 1
NATURAL GAS CONVERSION VIII 4
Copyright Page 5
Table of Contents 12
Preface 6
Program Committee 8
Organizing Committee 8
International Scientific Advisory Board 9
Financial Support 10
Part I. Catalytic combustion 24
Chapter 1. Catalytic combustion of methane over Pd/SBA-15/Al2O3/FeCrAl catalysts 24
Abstract 24
Key words 24
1. Introduction 24
2. Experimental 25
3. Results and discussion 25
4. Conclusion 28
Acknowledgements 29
References 29
Chapter 2. Catalytic Combustion of Methane over PdO-CeO2/Al2O3 and PdO-CeO2/ZrO2 catalysts 30
1. Introduction 30
2. Experimental 31
3. Results and Discussion 32
4. Conclusion 35
5. References 35
Part II. Direct conversion of methane to oxygenates, olefins and aromatics 36
Chapter 3. Methane conversion to chemicals, carbon and hydrogen (MCCH) over modified molybdenum-NAS catalysts 36
SUMMARY 36
INTRODUCTION 36
EXPERIMENTAL 37
RESULTS AND DISCUSSION 37
ACKNOWLEDGEMENT 39
REFERENCES 39
Chapter 4. Oxidative coupling of methane in a catalytic membrane reactor: Impact of the catalyst-membrane interaction on the reactor performance 42
1. Introduction 42
2. Experimental 42
3. Results and Discussion 43
4. Conclusions 47
Acknowledgements 47
References 47
Chapter 5. Characterization of Mo/ZSM-11 and Mo-Ru/ZSM-11 catalysts. Effect of Mo content and Ru addition on the nature of Mo species 48
1. Abstract 48
2. Introduction 48
3. Experimental 49
4. Results and discussion 49
5. Conclusions 53
6. Acknowledgements 53
7. References 53
Chapter 6. Conversion of methane to benzene via oxidative coupling and dehydroaromatization 54
Abstract 54
1. Introduction 54
2. Experimental 55
3. Results and Discussion 56
4. Conclusions 59
Acknowledgements 59
References 59
Chapter 7. Bimetallic orthophosphate and pyrophosphate catalysts for direct oxidation of methane to formaldehyde 60
1. Introduction 60
2. Experimental 61
3. Results and discussion 62
Acknowledgement 65
References 65
Part III. Energy production from natural gas 66
Chapter 8. IT-SOFC operated with catalytically processed methane fuels 66
Abstract 66
1. Introduction 66
2. Experimental 67
3. Results and Discussion 67
4. Conclusions 71
Acknowledgments 71
References 71
Part IV. FT synthesis of hydrocarbons 72
Chapter 9. Activity and stability of iron based catalysts in advanced Fischer-Tropsch technology via CO2-rich syngas conversion 72
Abstract 72
1. INTRODUCTION 72
2. EXPERIMENTAL 73
3. RESULTS AND DISCUSSIONS 73
4. CONCLUSIONS 77
References 77
Chapter 10. Highly active cobalt-on-silica catalysts for the Fischer-Tropsch synthesis obtained via a novel calcination procedure 78
1. Introduction 78
2. Experimental 79
3. Results and discussion 80
4. Conclusions 83
Acknowledgements 83
References 83
Chapter 11. Intensification of Commercial Slurry Phase Reactors 84
1. Introduction 84
2. Fundamental studies 85
3. Potential capacity for slurry phase reactors 87
4. Demonstration of slurry phase reactor capacity 88
5. References 89
Chapter 12. A Hydrodynamic Experimental Study of Slurry Bubble Column 90
1. MAIN TEXT 90
2. EXPERIMENTAL SET UP 91
3. RESULT AND DISCUSSION 92
4. CONCLUSION 94
REFERENCES 95
Chapter 13. H-ZSM-5/cobalt/silica capsule catalysts with different crystallization time for direct synthesis of isoparaffins: simultaneous realization 96
1. Introduction 96
2. Experimental 97
3. Results and Discussion 98
References 101
Chapter 14. Fischer-Tropsch catalyst deposition on metallic structured supports 102
Abstract 102
Keywords 102
1. Introduction 102
2. Experimental 103
3. Results and Discussion 104
4. Conclusions 107
Acknowledgments 107
5. References 107
Chapter 15. On the origin of the cobalt particle size effect in the Fischer-Tropsch synthesis 108
1. ABSTRACT 108
2. INTRODUCTION 108
3. EXPERIMENTAL 109
4. Catalyst preparation and characterization 109
5. RESULTS AND DISCUSSION 110
5. CONCLUSIONS 112
ACKNOWLEDGMENT 113
REFERENCES 113
Chapter 16. Modification of cobalt catalyst selectivity according to Fischer-Tropsch process conditions 114
Abstract 114
1. Introduction 114
2. Experimental 115
3. Results and discussion 115
4. Conclusion 119
Reference 119
Chapter 17. Effect of water on the deactivation of coprecipitated Co-ZrO2 catalyst for Fischer-Tropsch Synthesis 120
1. Introduction 120
2. Experimental 121
3. Results and discussion 122
4. Conclusion 125
References 125
Chapter 18. Effect of preparation methods on the catalytic properties of Co/SBA-15 catalysts for Fischer-Tropsch synthesis 126
Abstract 126
1. Introduction 127
2. Experimental 127
3. Results and discussion 128
4. conclusion 131
Acknowledgment 132
References 132
Chapter 19. Influence of pretreatment on the catalytic performances of Co-ZrO2 catalysts for Fischer-Tropsch synthesis 134
1. Introduction 134
2. Experimental 135
3. Results and discussion 135
4. Conclusion 139
Acknowledgment 139
References 139
Chapter 20. Fischer-Tropsch synthesis. Recent studies on the relation between the properties of supported cobalt catalysts and the activity and selectivity 140
Abstract 140
1. Introduction 140
2. Experimental 141
3. Results and Discussion 142
3. Conclusions 145
Acknowledgement 145
References 145
Chapter 21. Patenting Trends in Natural Gas Fischer-Tropsch Synthesis 146
Abstract 146
1. Introduction 147
2. Methodology 147
3. Results 148
4. Conclusion 151
Chapter 22. Cobalt Supported on Different Zeolites for Fischer-Tropsch Synthesis 152
ABSTRACT 152
1. Introduction 152
2. Experimental 153
3. Results and Discussion 153
4. Conclusions 157
Acknowledgments 157
References 157
Chapter 23. Production of liquid hydrocarbons employing Natural Gas: a study of the technical and economical feasibility of a GTL plant in Brazil 158
1. Introduction 158
2. Diesel fuel as the main product: high quality 160
3. Discussion 160
4. Economical analysis 161
5. Conclusion 163
6. Bibliography 163
Chapter 24. New Supports for Co-based Fischer-Tropsch Catalyst 164
1. INTRODUCTION 164
2. EXPERIMENTAL 164
3. RESULTS AND DISCUSSION 165
4. CONCLUSIONS 169
Acknowledgments 169
REFERENCES 169
Chapter 25. Fischer-Tropsch synthesis on Pd-Co/Nb2O5 catalysts 170
1. Introduction 170
2. Experimental 170
3. Results and Discussion 171
4. Conclusion 175
5. References 175
Part V. H2 production to fuel cells 176
Chapter 26. Methane Conversion for Fuel Cells. The Role of Sulphur 176
1. Reforming Technologies 176
2. The Impact of Sulphur 177
3. Conclusions 180
References 181
Chapter 27. Experimental Demonstration of H2 Production by CO2 Sorption Enhanced Steam Methane Reforming Using Ceramic Acceptors 182
1. Introduction 182
2. Experimental part 183
3. Results and Discussion 184
4. Conclusion 187
References 187
Chapter 28. Effect of support on autothermal reforming of methane on nickel catalysts 188
1. Introduction 188
2. Experimental 189
3. Results and Discussion 190
Conclusions 193
References 193
Chapter 29. Selective CO removal in the H2-rich stream through a double-bed system composed of non-noble metal catalysts 194
Abstract 194
1. Introduction 194
2. Experimental 195
3. Result and Discussion 196
4. Conclusion 198
Acknowledgement 199
References 199
Chapter 30. Hydrogen Production by Steam Reforming of Natural Gas over Highly Stable Ru Catalyst Supported on Nanostructured Alumina 200
1. Introduction 200
2. Experimental 201
3. Results and Discussion 202
References 205
Chapter 31. Heat effects in a membrane reactor for the water gas shift reaction 206
1. Introduction 206
2. Mathematical model 207
3. Results and Discussion 208
4. Conclusions 210
5. Nomenclature 211
6. References 211
Chapter 32. Au/ZnO and the PROX REACTION 212
1. Introduction 212
2. Experimental 213
3. Results and Discussion 214
4. References 217
Chapter 33. Selective Catalytic Oxidation of CO in H2 over Copper-Exchanged Zeolites 218
Abstract 218
Keywords 218
1. Introduction 218
2. Experimental 219
3. Results and discussion 220
4. Conclusions 223
5. References 223
Chapter 34. ZrO2-supported Pt Catalysts for Water Gas Shift Reaction and Their Non-Pyrophoric Property 224
1. Introduction 224
2. Experimental 225
3. Results and Discussion 226
References 229
Chapter 35. Steam reforming of natural gas on noble-metal based catalysts: Predictive modeling 230
1. Introduction 230
2. Experiment 231
3. Modeling approach 231
4. Results and Discussion 232
5. Predictive Modeling 233
6. Conclusions 235
Acknowledgements 235
References 235
Chapter 36. Activity of Cu/CeO2 and Cu/CeO2-ZrO2 for low temperature water-gas shift reaction 236
1. Abstract 236
2. Introduction 236
3. Experimental 237
4. Results and Discussion 238
5. Conclusions 241
Acknowledgements 241
References 241
Chapter 37. Hydrogen separation from the mixtures in a thin Pd-Cu alloy membrane reactor 242
1. Introduction 242
2. Experimental 243
3. Results and discussion 244
4. Conclusion 247
Acknowledgements 247
References 247
Chapter 38. Effect of cobalt on the activity of iron-based catalysts in water gas shift reaction 248
1. Introduction 248
2. Experimental 249
3. Results and Discussion 250
4. Conclusions 253
References 253
Part VI. Natural gas to chemicals 254
Chapter 39. The role of carbon nanospecies in deactivation of cobalt based catalysts in CH4 and CO transformation 254
ABSTRACT 254
1. INTRODUCTION 254
2. EXPERIMENTAL 255
3. RESULTS AND DISCUSSION 256
4. CONCLUSIONS 259
ACKNOWLEDGEMENTS 259
REFERENCES 259
Chapter 40. Effective and stable CeO2-W-Mn/SiO2 catalyst for methane oxidation to ethylene and ethane 260
ABSTRACT 260
Keywords 260
1. Introduction 260
2. Experimental 261
3. Results and discussion 261
4. Conclusion 264
5. Acknowledgments 265
References 265
Chapter 41. Very Large Scale Synthesis Gas Production and Conversion to Methanol or Multiple Products 266
Abstract 266
1. Introduction 266
2. Synthesis Gas and Methanol Technologies 267
3. Heat Exchange Reforming for Increased Single Line Capacity 270
4. Synthesis Gas Production for Multiple Products 270
References 271
Chapter 42. Autothermal Reforming of Methane under low Steam/Carbon ratio on supported Pt Catalysts 272
Abstract 272
1. Introduction 272
2. Experimental 273
3. Results and Discussion 274
4. Conclusion 277
Acknowledgements 277
References 277
Chapter 43. Conversion of natural gas to higher valued products: light olefins production from methanol over ZSM-5 zeolites 278
Abstract 278
1. Introduction 278
2. Experimental 279
3. Results and Discussion 279
4. Conclusions 283
Acknowledgements 283
References 283
Chapter 44. Lurgi’s Methanol to Propylene (MTP®) Report on a successful Commercialisation 284
The idea and the first steps 284
Propylene – Still an attractive product with high value 285
Lurgi’s Gas to Propylene (GTP® / MTP®) Technology 286
Commercialization has started 289
Conclusions 289
REFERENCES 290
Part VII. Production of synthesis gas 292
Chapter 45. Partial oxidation of hydrocarbon gases as a base for new technological processes in gas and power production 292
Abstract 292
1. Introduction 292
2. Low-scale methanol for preventing formation of gas hydrates 293
3. On-site production of methanol for sulphur removal 293
4. Processing of ethane fraction from associated and natural gas separation plants 293
5. Production of chemicals. Oxidative reforming of fat gases 294
6. Methanol production on power plants and decreasing NOx emission 294
7. Conclusions 296
References 297
Chapter 46. Effect of chemical treatment on Ni/fly-ash catalysts in methane reforming with carbon dioxide 298
1. Introduction 298
2. Experimental 299
3. Results and discussion 299
4. Conclusion 303
References 303
Chapter 47. Kinetic Depressing the Deposition of Carbon Species on Ni-Based Catalysts: La2O3 Adjusts the Reaction Rates of CO2 Higher than CH4 by Tuning 304
1. Introduction 304
2. Experimental 305
3. Results 306
4. Discussion 308
5. Conclusion 309
References 309
Chapter 48. Investigation of unsteady-state redox mechanisms over ceria based catalysts for partial oxidation of methane 310
1. Introduction 310
2. Experimental 311
3. Results and discussion 311
4. Conclusion 315
5. References 315
Chapter 49. Investigation by high throughput experimentation of ceria based catalysts for H2 purification and CO2 reforming of CH4 316
1. Introduction 316
2. HTE for investigating OSC of new ceria based material for hydrogen purification. Perspectives for HT investigation of adsorption phenomena 317
3. Instability of Pt/doped ceria catalysts for CO2 reforming of methane 319
4. Conclusion 321
Acknowledgements 321
5. References 321
Chapter 50. A Carbon Reaction Pathway for Dimethyl Ether, Methanol and Methane from Syngas on an Alumina Supported Palladium Catalyst 322
1. Abstract 322
2. Introduction 322
3. Modeling and Data Analysis 323
4. Results and Discussion 326
5. Conslusion 327
Reference 328
Chapter 51. Low Emission Conversion of Natural Gas to Hydrogen 330
Abstract 330
1. Introduction 330
2. Experimental 331
3. Results and Discussion 332
References 335
Chapter 52. SiC as stable high thermal conductive catalyst for enhanced SR process 336
1. Abstract 336
2. Introduction 336
3. Experimental 337
4. Results and discussion 338
5. Conclusions 341
References 341
Chapter 53. Catalytic partial oxidation of CH4 and C3H8: experimental and modeling study of the dynamic and steady state behavior of a pilot-scale reformer 342
1. Abstract 342
2. Introduction 342
3. Reactor and catalyst design 343
4. Results 344
5. Model analysis 345
6. Conclusion 347
References 347
Chapter 54. Additive effect of O2 on propane catalytic dehydrogenation to propylene over Pt-based catalysts in the presence of H2 348
1. Introduction 348
2. Experimental 348
3. Results and discution 349
4. Conclusions 353
References 353
Chapter 55. Au/TiO2 as a catalyst for the selective hydrogen combustion (SHC) applied to the catalytic dehydrogenation of propane 354
Abstract 354
Keywords 354
1. Introduction 354
2. Experimental 355
3. Results and discussion 356
4. Conclusions 359
Acknowledgements 359
References 359
Chapter 56. Oxidative dehydrogenation of ethane at short contact times 360
ABSTRACT 360
1. INTRODUCTION 360
2. EXPERIMENTAL 361
3. RESULTS AND DISCUSSION 361
4. CONCLUSIONS 365
ACKNOWLEDGEMENT 365
REFERENCES 365
Chapter 57. Study of synthesis gas production over structured catalysts based on LaNi(Pt)Ox- and Pt(LaPt)-CeO2-ZrO2 supported on corundum 366
1. Introduction 366
2. Experimental 367
3. Results and discussion 367
4. Conclusion 371
References 371
Chapter 58. Direct synthesis of Propane/Butane from synthesis gas 372
Abstract 372
1. Introduction 372
2. Results and discussion 373
3. Summary 377
Reference 377
Chapter 59. LPG Synthesis from DME with semi-direct method 378
Abstract 378
1. Introduction 378
2. Experimental 379
3. Results and discussion 379
4. Conclusion 383
Acknowledgements 383
Reference 383
Chapter 60. Performance of monolithic catalysts with complex active component in partial oxidation of methane into syngas: experimental studies 384
1. Introduction 384
2. Experimental 385
3. Modeling 385
4. Results and discussion 386
5. Conclusions 389
References 389
Chapter 61. CO2 reforming of methane to syngas over Ni/SBA-15/FeCrAl catalyst 390
Abstract 390
Key words 390
1. Introduction 390
2. Experimental 391
3. Results and discussion 391
4. Conclusions 395
Acknowledgements 395
Reference 395
Chapter 62. Scale-up Challenges in Synthesis Gas Production 396
1. Introduction 396
2. Use of CFD in Scaling Process 397
3. Adiabatic Reactors in Large Scale Plants 398
4. Some Aspects in the Reforming Section 399
5. Process Gas Waste Heat Section 399
6. Process Gas Exchange Reformer Option 400
7. Conclusion 401
References 401
Chapter 63. Studies of Carbon Deposition over Rh-CeO2/Al2O3 during CH4/CO2 Reforming 402
1. Abstract 402
2. Introduction 402
3. Experimental 403
4. Result and disscussion 404
Acknowledgements 407
References 407
Chapter 64. Development of CO2 Reforming Technology 408
Abstract 408
Introduction 408
Experimental 409
Results and Discussion 410
Conclusions 413
References 413
Chapter 65. The optimization of preparation, reaction conditions and synthesis gas production by redox cycle using lattice oxygen 414
ABSTRACT 414
1. INTRODUCTION 414
2. EXPERIMENTAL 415
3. RESULTS AND DISCUSSION 415
4. CONCLUSION 419
ACKNOWLEDGEMENTS 419
REFERENCES 419
Chapter 66. Effect of Rh addition on activity and stability over Ni/.-Al2O3 catalysts during methane reforming with CO2 420
ABSTRACT 420
1. INTRODUCTION 420
2. EXPERIMENTAL 421
3. RESULTS AND DISCUSSION 422
CONCLUSIONS 425
References 425
Chapter 67. Slurry Phase DME Direct Synthesis Technology-100 tons/day Demonstration Plant Operation and Scale up Study- 426
1. Introduction 426
2. Characteristics of DME direct synthesis and synthesis gas production 426
3. Operation results of 100 tons/day demonstration plant 428
4. Scale up of slurry phase reactor 429
5. Conclusion 431
Reference 431
Chapter 68. The performance of Pt/CeZrO2/Al2O3 catalysts on the partial oxidation and autothermal reforming of methane 432
Abstract 432
1. Introduction 432
2. Experimental 433
3. Results and Discussion 433
4. Conclusions 437
References 437
Chapter 69. Development of monolith catalyst for catalytic partial oxidation of methane 438
1. ABSTRACT 438
2. INTRODUCTION 438
3. EXPERIMENT 439
4. RESULTS and DISCUSSION 440
5. ACKNOWLEDGEMENTS 443
Chapter 70. Promoter effect of Ag and La on stability of Ni/Al2O3 catalysts in reforming of methane processes 444
Abstract 444
1. Introduction 444
2. Experimental 445
3. Results 446
4. Discussion 448
5. Conclusions 449
References 449
Chapter 71. The Effect of Pt Loading and Space Velocity on the Performance of Pt/CeZrO2/Al2O3 Catalysts for the Partial Oxidation of Methane 450
ABSTRACT 450
1. Introduction 450
2. Experimental 451
3. Results and Discussion 451
4. Conclusions 455
Acknowledgments 455
References 455
Chapter 72. Promoter effect of CeO2 on the stability of supported Pt catalysts for methane-reforming as revealed by in-situ XANES and TEM analysis 456
Abstract 456
1. INTRODUCTION 456
2. EXPERIMENTAL 457
3. RESULTS AND DISCUSSION 458
4. CONCLUSIONS 461
ACKNOWLEDGEMENTS 461
REFERENCES 461
Chapter 73. Advanced Auto-thermal Gasification Process 462
ABSTRACT 462
1. INTRODUCTION 462
2. A-ATG PROCESS 463
3. RESULTS AND DISCUSSION 465
4. CONCLUSION 467
REFERENCES 467
Chapter 74. Bifunctional Catalysts for Hydrogen Production from Dimethyl Ether 468
Abstract 468
1. Introduction 468
2. Experimental 469
3. Results and Discussion 470
4. Conclusion 473
References 473
Chapter 75. Autothermal reforming of methane over nickel catalysts prepared from hydrotalcite-like compounds 474
1. Introduction 474
2. Experimental 475
3. Results and Discussion 476
4. CONCLUSIONS 479
REFERENCES 479
Chapter 76. A high effective catalytic system for the production of synthesis gas for gas-to-liquid 480
1. Introduction 480
2. Experimental 481
3. Results and Discussion 481
4. Conclusions 485
References 485
Chapter 77. Conversion of methanol to hydrocarbons: Hints to rational catalyst design from fundamental mechanistic studies on H-ZSM-5 486
1. Introduction 486
2. Experimental 487
3. Results and discussion 488
References 491
Chapter 78. Dry Reforming and Partial Oxidation of Natural Gas to Syngas Production 492
Abstract 492
Keywords 492
1. Introduction 492
2. Experimental 493
3. Results 493
4. Conclusions 497
Acknowledgements 497
References 497
Chapter 79. Preparation of Ni/SiO2, Ni/SiO2-CaO and Ni/SiO2-MgO catalysts for methane steam reforming 498
1. Introduction 498
2. Experimental 499
3. Results and Discussion 500
4. Conclusions 503
5. References 503
Chapter 80. Perovskites as catalyst precursors: partial oxidation of methane on La1-xCaxNiO3 504
1. Introduction 504
2. Experimental 505
3. Results and Discussion 506
4. Conclusions 509
References 509
Chapter 81. Ni/CeZrO2-based catalysts for H2 production 510
Abstract 510
1. Introduction 510
2. Experimental 511
3. Results and Discussion 511
4. Conclusions 515
Acknowledgments 515
References 515
Chapter 82. Effect of aluminum content on the properties of lanthana-supported nickel catalysts to WGSR 516
1. Introduction 516
2. Experimental 517
3. Results and Discussion 518
4. Conclusions 521
References 521
Chapter 83. Evaluation of Pd/La2O3 catalysts for dry reforming of methane 522
1. Introduction 522
2. Experimental 523
3. Results and Discussion 524
4. Conclusions 527
References 527
Chapter 84. SNOW: Styrene from Ethane and Benzene 528
1. Introduction 528
2. The innovative SNOW technology 529
3. SNOW Technology development steps 532
4. Final considerations 532
Acknowledgements 533
References 533
Chapter 85. Designing Pt catalysts by sol-gel chemistry: influence of the Pt addition methods on catalyst stability in the partial oxidation of methane 534
Abstract 534
1. INTRODUCTION 534
2. EXPERIMENTAL 535
3. RESULTS AND DISCUSSION 535
4. CONCLUSION 539
5. REFERENCES 539
STUDIES IN SURFACE SCIENCE AND CATALYSIS 540